Monoazo dyestuffs



Patented June 28, 1949 STATES? MONOA'ZO' DYESTUFFS Basil 'Jason I-Ieywood; Blackley, Manchester, England, assignor to Imperial Chemical Industries Limited, lalcorporationlof Great Britain? No Drawing. Application August 3, 1945, Serial No. 608,842; In Great BrItainAuguSt ZS, 1944..

4 Claims. (01. 260 -205) This invention; relates to. new monoazor dyestuffs; more particularly to: new monoazo dyestuffs-suitableefor dyeing, synthetic fibres suchwas. cel-lulosea acetate artificial! silk, and nylon;

According: to the present invention new monoazo dyestuiis aremade-bya processvcomprising coupling a diazotised p-nitroaniline which may carry substituentssotherrthan sulphonic acid, carboxylic acid oncyano groups, with the sulphuric ester of-an N hydroxyalkyleN-phenylor naphthyr-alkyl (2; 3" or 4 carbon atoms) aniline which-may carry further substituents other than sul'phonicacid or carboxyl substituents subject to its being capableof-coupling' in the para-position to-the nitrogen atom.-

Accordi'ngto afiirther feature of this inventionthe sametmonoazo, dyestuffs are made by usingascoupling component the" N-hydroxyalkyl N phenyl" or? naphthyl alkyl (2, 3 or- 4 carbon atoms) aniline'in place ofits sulphuric ester and subsequently converting" the resulting hydroxyalkyl-monoazo com-pound to-its'sulphuric esterby treatment with sulphuric acid or other known agent suited to yield fits-sulphuric ester.

Examples of nitroarylamines are:

p-nitraniline.

2 rchloroell-nitranilme 2=br0mo=4enitroani1ine 2 5rdich1or-4-nitramlinel- 2,26dichlorr lenitraniline 2 6edibrom-ll-nitraniline. 2.-,brom-fi chlorr-nitraniline 6 -chlor.-2 4.-dinitraniline 6,-bromoe2g4vdinitroanilinel 2 :A-dinitraniline 5-I1it10n2-3H1i110311i5013. 5enitro-2r-aminotoluene By Way" of an N hyclroxyalkyl N-'aryl alkyl (2;- 3 or 4*oarbon atoms) '-ani1in'e there=maybe employed, e: g.

2 N-- p1 phenylethyll- N [i hydroxy-nspropyl aniline a N. ,6. p henylethyl -N e hydroxy-neamyL aniline:

L -fl y y thyhblw'-phenylethylaniline fl ydroxy yl N- 6 naphthy1 (2.);-

ethylaniline N-p-hydroXyethyI-N B -p=tolylethylaniline The new dyestuffs, in the: form'of 'theirjalkali metal or. ammonium saltaare soluloleinwaterf and. havevery good afiinity for cellulose acetate artificial silk which they dye from a neutral? slightly acid; or slightly alkaline dyebath aiford inggviolet, brown; orange; crimson and red shades: Theseshades are of good fastness, are discharge= able; and are suitable for printing cellulose acetate artificial silk; The new dyestufisare; moreover, generally suitable for applicationto" acetate artificial. silk from" dilute or long yllquorsf such. as are employed in dyeingwith the winch? machine.

The; new dyestuffs are also valuable for the" dyeing of" wool; naturalsilk; tin weightedisil'ka leather and linear superpolyamide fibres such as" nylon:

The application of" the" new dyestuffs to"th"e" colouring'of synthetic fibres,forexample cellulose?" acetate. artificial silk and linear superp'olyamidesi suclras: nylon, constitutes astillfurther feature of 'Ithe invention;

The invention isi1lustrated;ldutinot limited; by" thepfollowing examples'in whiohthe parts areby" weight;

Example 1 A fine suspension of 13.8, pa-rts of p-nitroaniline in 400 parts of water and 36..parts of36 hydrochloric acid is":diazotised by the addition of 6.9

parts of sodium nitrite dissolved in parts of water: 'llhetflltered solution of'z'thed-iazo loompound, ,cooleduto.-5 Grisaslowly: added to a simi larlyrcooled-f and; stirred. solutiom of 34w3upalfitm0fh the sodiumwsalt" of- N fl hydroxyethylm- Nw-- 3 phenyleethylaniline sulphuricv ester" in'w400 partsofiwater. Aiter stirring the"mixture-forone'houn: one:completes-thei-coupling by-adding sufiicientx 50%? aqueous" sodium? acetate to remove them mineralr acidity of the suspension. The-- suspene sionof thevmonoazotdyestufi is then-rendered=l justu alkaline to Brilliant Yellow by the additioniof-5- N sodium hydroxide solution. The dyestufl' is filtered off, Washecl'witlr'2' aqueous sodium chlorider-solutiontandldried at 30-40 Or The: i new dyestufis forms a dark red; powder N p hydroxyethyl N [3 phenylethylaniline sulphuric ester is obtainable by causing N-p-phenylethylaniline to react with ethylene chlorohydrin in boiling aqueous suspension in the presence of chalk to give N-fl-hydroxyethyl-N- [BC-phenylethylaniline (boiling point 223-30/14 min.) which is converted to its sulphuric ester by treatment with chlorosulphonic acid in tetrachloroethane. N--fi-phenylethylaniline is obtained by heating aniline with p-phenylethyl bromide.

Example 2 13.8 parts of p-nitroaniline are diazotised as in Example The solution of the diazo compound, cooled to. 5-l0 0., is then gradually added with stirring to a similarly cooled solution of 35.7 parts of the sodium salt of N-fi-hydroxyethyl-N-V- phenylpropylaniline sulphuric ester in 400 parts of water. After stirring the mixture for 2 hours, sufficient 50% aqueous sodium acetate is added to remove the mineral acidity of the coupling.

medium. Stirring is continued until coupling is complete. The suspension of the monoazo dyestuif is then rendered just-alkaline to Brilliant Yellow by the addition of 5 N aqueous sodium hydroxide. The dyestufi is filtered oil, washed with 2 /2% aqueous sodium chloride and dried at 30-40 C The new dyestuff forms a dark red powder which dissolves in water with a red colour and in sulphuric acid with a reddish brown colour. It dyes cellulose acetate artificial silk in scarlet shadeswhen applied from a neutral dyebath containing Glaubers salt or sodium chloride, the dyeings exhibiting good fastness to wet treatments and to light, good dischargeability and freedom from sublimation. The new dyestuff is represented by the following formula:

CHz-CHa-O-S 0 H CHrCHz-CHrO N p-hydroxyethyl N v phenylpropylaniline sulphuric ester is obtainable by causing N-yphenylpropylaniline to react with ethylene chlorohydrin in boiling aqueous suspension in the presence of chalk to give N-B-hydroxyethyl-N- 'y" phenylpropylaniline (boiling point 237-40" C./14 mins.) which is converted into its sulphuric ester by treatment with chlorosulphonic acid in tetrachloroethane. -N-v-phenyl-propylaniline is obtained by heating aniline with 'y phenyl npropylbromide.

Example 3 A fine suspension of 17.3 parts of o-chloro-pnitroaniline in-300 partsof water and 30"parts of 36% hydrochloric acid is diazotised by the addi tion of 6.9 parts of sodium nitrite dissolved in 50 parts of water. The filtered solution of the diazo compound, cooled to 5 C., is slowly added to a similarly stirred and cooled solution of 34.3 parts of the sodium salt of N-p-hydroxy-ethyl-N-B phenylethylaniline sulphuric'ester dissolved in 40 0 parts of water. After stirring for one hour sufiicient 50% aqueous sodium acetate is added to remove the mineral acidity of the coupling medium. The, suspension is stirred until the coupling is complete. The suspension of the monoazo dyestuif is then made slightly alkaline to Brilliant Yellow by the addition of 5 N aqueous sodium hydroxide. The dyestuff is filtered off, washed with 2 /2% aqueous sodium chloride solution and dried at 30-40 C.

The new dyestuff forms a dark greenish powder which dissolves in water with a red colour and in concentrated sulphuric acid with a brown colour. It dyes cellulose acetate artificial silk and nylon in crimson shades When applied from a neutral dyebath containing Glaubers salt or sodium chloride, the dyeings exhibiting good fastness to wet treatments and to light, good dischargeability and freedom from sublimation.

Example 4 In Example 3 35.7 parts of the sodium salt of N-p-hydroxyethyl-N-v'-phenylpropylaniline sulphuric ester are used in place of the 343 parts of the sodium salt of N B hydroxyethyl-N iiphenylethylaniline sulphuric ester.

The new dyestuff forms a dark greenish powder which dissolves in hot water to a red solution and in concentrated sulphuric acid to a reddish brown solution. It dyes cellulose acetate artificial silk from a neutral or slightly alkaline dyebath containing Glaubers salt or sodium chloride in red shades, the dyeings having good fastness to Wet treatments and to light. It is also well suited for printing cellulose acetate artificial silk.

Example 5 13.8 parts of p-nitroaniline are diazotised as in Example 1. The solution of the diazo compound. cooled to 5-10" C. is then gradually added to a cooled and stirred solution of 35.7 parts of the sodium salt of N-B-hydroxyethyl-N-B-phenylethyl-m-aminotoluene sulphuric ester in 400 parts of water containing suflicient sodium carbonate to keep the mixture alkaline to Brilliant Yellow. The suspension of the monoazo dyestuff so obtained is stirred for two hours. The dyestufi is then filtered off, washed with 2.5% aqueous sodium chloride and dried at 30-40" C.

The new dyestuif is a dark red powder which dissolves in water to give a red. solution and in sulphuric acid to give a dull yellow solution. It

dyes cellulose acetate artificial silk in crimson shades when applied from a neutral dyebath containing Glaubers salt or sodium chloride. and the dyeings exhibit good fastness to wet treat ment and to light, good dischargeability and freedom from sublimation.

N-B-hydroxyethyl N-B'-phenylethyl-m-amino toluene sulphuric ester is obtainable by causing N-e-hydroxyethyhm-toluidine to react with pphenylethyl bromide in boiling aqueous suspension in the presence of chalk to give N-{i-hydroxyethyl-N-p-phenylethyl-m-aminotoluene (boiling point 216-220 0/20 min.) which is then convertedinto its sulphuric ester by treatment with chlorosulphonic acid in ethylene dichloride solu- Example 6 In the process described in Example 5, 38.75 parts .of the: sodium salt of N-p-hydroxyethyl N- 9-pheny1ethyl-m-chloroaniline sulphuric ester are usedin the "place ofthe 35.2? :parts .or the sodium :salt :of N-p-hydroxyethyl-Np"aphenylethyLm-aminotoluene sulphuric ester.

The new dyestuff is a redpowder which dissolves in hot water to give a red solution and in concentrated sulphuric acid to give an orange brown solution. iIt dyes cellulose acetate .artificial silk and nylon from a neutral or slightly alkaline dyebath containing Glaubers salt or sodium chloride in scarlet shades, the dyeings havinggood fastness to wet treatmentsand to light. It is also well suited for'printing cellulose acetate artificial silk. The new dyestuif is represented by the following lformula:

N-s-hydroxyethyl N-p'-phenylethyl m chloroaniline sulphuric estermaybe attained by causing N-p-hydroxyethyl-m-cliloroaniline to react with .e-phenylethyl bromide in boiling aqueous suspension in the presence of chalk to give N-B- hydroxyethyl-N-fi-phenylethyl-m chloroaniline (B. P. 180-97 C./0.l min.) which is convertedinto its sulphuric ester by treatment with chlorosulphonic acid in ethylene dichloride solution.

Example 7 In the process describedinExample 5, 37.3 parts of the sodium salt of N-p--hydroxyethyl-N-j3- phenylethyl-m-amino anisole sulphuric esterare used inthe place of.the.35.7 parts of the sodium salt of N p? -hydroxyethyl-Nefl"-phenylethyl-maminotoluene sulphuricester.

The new dyestuff is a black powder which dissolves hotwater to ,give a crimson solution and in concentrated sulphuric acid to give a reddish brown colouration. It dyes cellulose acetate artificial silk and nylon in crimson shades when applied from a neutraldye'bath containingGlaubers salt or sodium chloride, .the dyeings exhibiting good fastness to wet treatments and to light, good dischargeability and freedom from sublimation. It isalso well suitedror printing cellulose acetate artificial silk. The new dyestufi is represented by the following formula:

N -p hydroxyethy-l N- e -phenylethyl -mamino-anisole sulphuric ester may be obtainedby causing N-B-hydroxyethyl-m-aminoanisole toreact with ,d-phenylethyl bromide rln-boilingaqueous suspension "in the-presence of chalk to give N-phydroxyethyl-N-e-phenylethyl-m aminoanisole (boiling point 210 C./ 1.5 min.) which is converted into its sulphuric acid ester by treatment with chlorosulphoni'c acid in ethylene dichloride solution. l i l Example 8 .2037 :parts of 2:'6.@dichloro-4-nitroaniline are diazotisedmy gradual:addition to a solution of 6.9 pants of dry sodium nitrite in 148;partsof concentrated sulphuric acid. The sulphuric acid solution is stirred for 1-2 hours and is then added to 400 parts of ice and :parts of water. The filtered solution of the diazo compound so obtained is added gradually to an ice cold solution of 34.3

'parts ofthe sodium salt'oi N-p-hydroxyethyl-N- p-phenylethyl-aniline-sulphuricester in 400 parts of water. Simultaneously with the addition of the sdi'azo sol-ution 40 aqueous sodium hydroxide is added at such a rate as to keep the coupling -mix-ture 'faintly acid to Congo red paper. The

temperature or the coupling mixture is kept throughout the coupling at 0-'5 C. by the addition as necessar yaof ice. When all the diazo solution has been added the mixture is made alkaline to litmus by the addition of aqueous sodium hydroxide. The dyestufl is then filtered off and dried.

Themew dyestufi is a dark .brown powder which dissolvesinhotwaterto .give an orange brown solutionand in sulphuric acid togive a dull brown solution.

It dyes cellulose acetate artificial silk and nylon in .orange brown shades when applied from a neutral dyeba'th --containing Glaubers salt or sodium cl'iloride; the vdyeings exhibit good fastnessto wet treatments and to light, good dischargeability and :freedom from sublimation. The new dyestufi. is -we1l.suited to the dyeing oi cellulose .acetate artificial silk from dilute or long liquor ldyebathssuch as are employed in dyeing with the winch.

Example 9 19parts of 2*:4- dinitroaniline are diazotised by means .of nitrosyl sulphonic acid in'lconcentrated sulphonic acid solution in the known way and the aqueoussolution of the diazo compound obtained by pouring the sulphuric acid solution on to ice, is added to a solution of 34.5.parts of the sodium salt of 'N-B-hydroxyethyl-N-p-pheny1ethyl-anilinesulphurices'ter; in 400 parts of water. Simultane'ously' with the addition of' the diazo solution, 40% 'aque'ousisodium hydroxide solution is added at such a rate as'to keep the coupling mixture faintly acid ftoCongo red paper. The temperature lot the "coupling mixture is kept at 0-5 C. throughoutthecouplingby the addition as necessary of ice. Whenejllthe diazo solution has been i added 'themixture is'made alkaline to litmus by the addition'ofsodium hydroxide solution. The suspension "is stirred "for several hours and the dyestulf is then filtered off, washed and dried.

The new dyestuff is a dark brown powder which dissolves'inhot waterto give aviolet solution and in sulphuricacidto give a violet solution. It dyes cellulose acetate artificial silk in reddish violet shades "whenapplied from a'neutral dyebath containing Glaubers salt or sodium chloride, and the dyeings "exhibit good fastness to wet treatments and to flight- Example 10 21375 parts :of 6-chloro-2:4-dinitroaniline are graduallyradded ito a solution of 6.9 parts of sodimnmitriteindm parts 'of'su'lphuric acid. The resulting'solution is warmed to 50-55 C. and kept at that temperature for :two hours. It is then cooled tol 20- 25C.'and =added :slowlyto a stirred and "cooled solution of 35.7 parts of the sodium salt of iN-p hydroxylethyl N+flfiphenylethyl m 7. aminotoluene sulphuric ester in 400 parts of water. Simultaneously with the addition of the diazo solution, 40% aqueous sodium hydroxide is added at such a rate as to keep the coupling mixture 8 dyestuff of Example 1 and is believed to be idemcal with that dyestufi.

In the following examples the dyestuffs may be made by the processes described in the preceding faintly acid to Congo red paper. The tempera- 5 examples:

Shade on Celg Diczo Component Coupling Component lulose acetate artificial silk p-nitroaniline N-fl-hydroxyethyl-N-fl-p-tolylethylaniline sulphuric ester Scarlet. 2:6-dichloro-4-nitroaniline 0 Orange brown. 2:6-dibromo-4-nitroaniline do Do. p-nitroaniline l. N-fl-hydroxyethyLlN-fl l-naphthyl) ethylanihne sulphuric est Scarlet. N- -hydroxypro'pyl-fl'-phenylethylaniline sulphuric ester Do. N-n-fl-hydroxypropyl-B-phenylethylaniline sulphuric ester- Do. N-fl-hydroxyethyLN fl phenylethylaniline sulphuric ester Crimson 2:4-Dinitroaniline do Violet 2:6 dibromo-4-nitroani1ine. p-nitro aniline 2-chloro-4-nitroaniliue 2:4-dinitr0ani1ine zzfi-dichloroi-nitroaniline 6-Bromo-2z4-dinitroaniline.

. do: I I NiB-hydroxyethyl-N-B-phenylethyl-2-methoxy-5-methylaniline sulphuric es- Orange brown. Scarlet. Crimson.

. Reddish violet. Orange brown. Reddish blue.

ture of the coupling mixture is maintained at 0-5 C. by the addition as necessary of ice. When all the diazo solution has been added, suflicient aqueous sodium hydroxide is added to render the coupling mixture alkaline to litmus. The resulting suspension is stirred for 12 hours, when the new dyestufi is isolated and dried.

It is a black powder which dissolves in hot water to give a bluish violet solution and in sulphuric acid to give a reddish brown solution. It dyes cellulose acetate artificial silk in bluish violet shades when applied from a neutral dyebath containing Glaubers salt or sodium chloride and the dyeings exhibit good fastness to wet treatments and to light. The new dyestuff is represented by the following formula:

CHz.CHi-O.S 0111 N02 CH3 Example 11 13.8 parts of p-nitroaniline are diazotised as described in Example 1 and the diazo solution is added to a cooled and stirred solution of 24.1 parts of N-c-hydroxy-ethyLN-B-phenylethylaniline in 400 parts of water containing 12 parts of 36% hy drochloric acid. The mixture is stirred for one hour then suflicient 50% aqueous sodium acetate to remove the mineral acidity is added of the coupling medium. The suspension of the monoazo compound so obtained is then rendered just alkaline to Brilliant Yellow by the addition of N aqueous sodium hydroxide. The monoazo compound is filtered off, washed with water and dried at 30-40 C.

The powdered water-insoluble monoazo compound obtained in the manner described above is converted into its sulphuric ester by gradual addition to 150 parts of 75-95% sulphuric acid. The resulting solution is stirred for 18 hours and then poured on to a stirred mixture of ice and water. The mixture is then stirred for one how and the dyestufi is filtered off and washed with water. It is then re-suspended in 400 parts of water and sufficient aqueous sodium hydroxide solution is added to make the suspension alkaline to Brilliant Yellow. The sodium salt of the new dyestuff so obtained is filtered off and dried at 30-40 C.

The new dyestufi is a dark red powder which dissolves in water to give a scarlet solution and in sulphuric acid to give a dull red solution. It possesses dyeing properties similarto those of the I claim: l. A monoazo dyestufi? represented by the formula i I 201112) MO wherein R and X are selected from the group consisting of H, CH3, -OCH3, Cl, Br and NO2, Y and Z are selected from the group consisting of I-I, -CH3, -OCl-I3 and --Cl, n is an integer from 1 to 4, and m is an integer from 1 to 3.

2. A monoazo dyestufi represented by the formula 3. A monoazo dyestufi represented by the formula CzHi-O-SOaH 4. A monoazo dyestuff represented by the formula BASIL JASON HEYWOOD.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,483,084 Green Feb. 12', 1924 2,045,323 Felix June 23, 1936 2,069,836 Knight Feb. 9, 1937 2,088,327 Knight July 27, 193 2,117,733 Krzikalla May 1'7, 1938 FOREIGN PATENTS Number Country Date 441,884 Great Britain Jan. 27, 936 833,141 France July 11, 1938 

